A1-pyrrolines

ABSTRACT

This invention relates to novel Δ 1 -pyrrolines of formula(I)  
                 
in which 
         R 1 , R 2 , Y and R 3  are as defined in the disclosure, to a number of processes for preparing these substances, and to their use for controlling pests.

The present invention relates to novel Δ¹-pyrrolines, to a number ofprocesses for them, and to their use as pesticides.

It is already known that many Δ¹-pyrrolines possess insecticidalproperties (cf. WO 00/21958, WO 99/59968, WO 99/59967 and WO 98/22438).The activity of these substances, although good, leaves a certain amountto be desired in some cases. The invention now provides novelΔ¹-pyrrolines of the formula (I)

in which

-   -   R¹ is halogen or methyl,    -   R² is hydrogen or halogen,    -   Y is O (oxygen) or S (sulphur),    -   R³ is C₁-C₄-alkyl, C₃-C₆-cycloalkyl or        C₃-C₆-cycloalkyl-C₁-C₂-alkyl.

Depending on the type and number of substituents, the compounds of theformula (I) may where appropriate be present in the form of geometricaland/or optical isomers or regioisomers or isomer mixtures thereof invarying compositions. Both the pure isomers and the isomer mixtures areclaimed by the invention.

It has additionally been found that A¹-pyrrolines of the formula (1) canbe prepared by a process in which

-   -   A) Δ¹-pyrrolines of the formula (II)        in which    -   R¹ and R² are as defined above and    -   Z is chlorine, bromine, iodine, —OSO₂CF₃ or —OSO₂(CF₂)₃CF₃,    -   are reacted in a tandem reaction with heterocycles of the        formula (III)        in which    -   Y and R³ are as defined above and    -   X is chlorine, bromine, iodine, —OSO₂CF₃ or —OSO₂(CF₂)₃CF₃,    -   in the presence of a catalyst, in the presence of a diboronic        ester and, where appropriate, in the presence of an acid binder        and, where appropriate, in the presence of a diluent or    -   B) Δ¹-pyrrolines of the formula (IV)        in which    -   R¹ and R² are as defined above and    -   A is —B(OH)₂, (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,        (5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,        (4,4,6-trimethyl-1,3,2-dioxabo-rinan)-2-yl or        1,3,2-benzodioxaborol-2-yl,    -   are reacted with heterocycles of the formula (III)        in which    -   Y, R³ and X are as defined above    -   in the presence of a catalyst, where appropriate in the presence        of an acid binder and where appropriate in the presence of a        diluent, or    -   C) Δ¹-pyrrolines of the formula (II)        in which    -   R¹, R² and Z are as defined above,    -   are reacted with boronic acid derivatives of the formula (V)        in which    -   Y, R³ and A are as defined above,    -   in the presence of a catalyst, where appropriate in the presence        of an acid binder and where appropriate in the presence of a        diluent or    -   D) Δ¹-pyrrolines of the formula (II-a)        in which    -   R¹ and R² are as defined above,    -   Z¹ is bromine or iodine,    -   are reacted with organometallic compounds of the formula (VI)        in which    -   Y and R³ are as defined above and,    -   M is ZnCl, Sn(Me)₃ or Sn(n-Bu)₃,    -   in the presence of a catalyst, where appropriate in the presence        of an acid binder and where appropriate in the presence of a        diluent.

Finally, it has been found that the compounds of the formula (I)according to the invention possess very good insecticidal properties andcan be used both in crop protection and in the protection of materialsfor controlling unwanted pests, such as insects.

A general definition of the Δ¹-pyrrolines of the invention is given bythe formula (I).

Preferred Δ¹-pyrrolines are those of the formula (I), in which

-   -   R¹ is fluorine, chlorine or methyl,    -   R² is hydrogen, fluorine or chlorine,    -   Y is O (oxygen) or S (sulphur),    -   R³ is C₁-C₄-alkyl, C₃-C₆-cycloalkyl or        C₃-C₆-cycloalkyl-C₁-C₂-alkyl.

Particularly preferred Δ¹-pyrrolines of the formula (I) are those inwhich

-   -   R¹ is fluorine or chlorine,    -   R² is hydrogen, fluorine or chlorine,    -   Y is O (oxygen) or S (sulphur),    -   R³ is methyl, ethyl, propyl, butyl, cyclopropyl, cyclobutyl,        cyclopentyl, cyclohexyl, cyclopropyl-C₁-C₂-alkyl,        cyclobutyl-C₁-C₂-alkyl, cyclopentyl-C₁-C₂-alkyl or        cyclohexyl-C₁-C₂-alkyl.

Very particularly preferred Δ¹-pyrrolines of the formula (I) are thosein which

-   -   R¹ is fluorine or chlorine,    -   R² is hydrogen or fluorine,    -   Y is O (oxygen) or S (sulphur),    -   R³ is methyl, ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl,        sec-butyl, tert-butyl, cyclopropyl, cyclobutyl, cyclopentyl,        cyclohexyl, cyclopropylmethyl, cyclobutylmethyl,        cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl,        cyclobutylethyl, cyclopentylethyl or cyclohexylethyl.

Further preferred Δ¹-pyrrolines of the formula (I) are those in which R¹and R² are fluorine.

Further preferred Δ¹-pyrrolines of the formula (I) are those in which Yis oxygen.

Further preferred Δ¹-pyrrolines of the formula (I) are those in which Yis sulphur.

Further preferred Δ¹-pyrrolines of the formula (I) are those in which R³is C₁-C₄-alkyl.

Very particular preference is given to (R)-configured compounds of theformula (I-a)

in which

-   -   R¹, R², Y and R³ are as defined above.

Compounds of the formula (I-a) are obtained by conventional methods ofracemate cleavage, such as, for example, by chromatography of thecorresponding racemates on a chiral stationary phase. In this way it ispossible to break down either the racemic end products or racemicintermediates into the two enantiomers.

Saturated hydrocarbon radicals such as alkyl may where possible in eachcase be straight-chain or branched.

The general definitions of radicals and elucidations set out above, orthose set out in ranges of preference, may also, however, be combinedwith one another, thus including any combinations between the respectiveranges and the ranges of preference. They apply correspondingly to theend products and also to the precursors and intermediates.

Using 5-(2,6-difluorophenyl)-2-(4-bromophenyl)-3,4-dihydro-2H-pyrrole,N-5-bromo-2-ethoxy-pyridine and4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane as startingmaterials, plus a palladium catalyst, the course of process (A) of theinvention can be illustrated by the following formula scheme.

Using5-(2,6-difluorophenyl)-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)-phenyl]-3,4-dihydro-2H-pyrroleand 5-bromo-2-isopropoxy-pyridine as starting materials, plus apalladium catalyst, the course of process (B) of the invention can beillustrated by the following formula scheme.

Using5-(2,6-difluorophenyl)-2-[4-(trifluoromethylsulphonyloxy)phenyl]-3,4-dihydro-2H-pyrroleand 2-ethoxy-5-pyridinylboronic acid as starting materials, plus apalladium catalyst, the course of process (C) of the invention can beillustrated by the following formula scheme.

Using 5-(2,6-difluorophenyl)-2-(4-bromophenyl)-3,4-dihydro-2H-pyrroleand 2-ethoxy-5-(tributylstannyl)pyridine as starting materials, plus apalladium catalyst, the course of process (D) of the invention can beillustrated by the following formula scheme.

Elucidation of the Processes and IntermediatesProcess (A)

In a first reaction step a compound of the formula (II) is coupled witha diboronic ester in the presence of a palladium catalyst, whereappropriate in the presence of an acid binding agent and whereappropriate in the presence of a solvent. In a second reaction step,without isolating the intermediate and in the same reaction vessel, acompound of the formula (III) is coupled in the presence of a catalyst,where appropriate in the presence of an acid binding agent and whereappropriate in the presence of a solvent (cf. e.g. Tetrahedron Lett.1997, 38, 3841).

Process (A) of the invention can be conducted in two variants. Either acompound of the formula (II) or a compound of the formula (III) can beintroduced initially. Process (A) can be regarded as a tandem reactionof processes (B) and (C) described below.

A general definition of the Δ¹-pyrrolines required as starting materialswhen carrying out process A of the invention is given by the formula(II). In this formula R¹ and R² stand preferably, with particularpreference or with very particular preference for those definitionswhich have already been given as preferred, particularly preferred, etc.for these radicals in connection with the description of the substancesof the formula (I) according to the invention. Z is preferably bromine,iodine, —OSO₂CF₃ or —OSO₂(CF₂)₃CF₃, with particular preference bromine,—OSO₂CF₃ or —OSO₂(CF₂)₃CF₃, with very particular preference bromine or—OSO₂CF₃.

Δ¹-Pyrrolines of the formula (II) can be prepared by known processes(cf. WO 98/22438).

A general definition of the heterocycles required as starting materialswhen carrying out process (A) of the invention is given by the formula(III). In this formula Y and R³ stand preferably, with particularpreference or with very particular preference for those meanings whichwere already mentioned as preferred, particularly preferred, etc. forthese radicals in connection with the description of the substances ofthe formula (I) according to the invention. X is preferably bromine,chlorine, iodine or —OSO₂CF₃, with particular preference bromine,chlorine or iodine, with very particular preference bromine or chlorine.

The heterocycles of the formula (III) are known or can be prepared byknown processes (cf. Aust. J. Chem. 1964, 17, 794; Chem. Ber. 1992, 125,1169; Chem. Pharm. Bull. 1995, 43, 247; Eur. J. Med. Chem. 1989, 24,249; J. Chem. Soc. C 1971, 1889; J. Chem. Soc. Perkin Trans. 1 1995,2497; J. Med. Chem. 1991, 34, 315; J. Org. Chem. 1984, 49, 2240; J. Org.Chem. 1990, 55, 69; Org. Prep. Proced. Int. 1998, 30, 433; Synthesis1999, 1163; Tetrahedron 1999, 40, 7975; Tetrahedron Lett. 1996, 37,4447; Tetrahedron Lett. 2000, 41, 4335).

Suitable diboronic esters when carrying out process (A) of the inventioninclude 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane,5,5,5′,5′-tetramethyl-2,2′-bi-1,3,2-dioxaborinane,4,4,4′,4′,6,6′-hexamethyl-2,2′-bi-1,3,2-dioxaborinane or2,2′-bi-1,3,2-benzodioxaborole. Preference is given to using4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane,5,5,5′,5′-tetramethyl-2,2′-bi-1,3,2-dioxaborinane or4,4,4′,4′,6,6′-hexamethyl-2,2′-bi-1,3,2-dioxaborinane, with particularpreference 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane or5,5,5′,5′-tetramethyl-2,2′-bi-1,3,2-dioxaborinane, with very particularpreference 4,4,4′,4′,5,5,5′,5′-octamethyl-2,2′-bi-1,3,2-dioxaborolane.

Process (A) of the invention is carried out using generally 1 mol or aslight excess of a diboronic ester and 1 mol or a slight excess of acompound of the formula (III) per mole of compound of the formula (II),plus 3% of a palladium catalyst. It is also possible, however, to usethe reaction components in other proportions. Either the compound of theformula (II) or the compound of the formula (III) can be introducedinitially. Working up takes place by conventional methods. The generalprocedure is to dilute the reaction mixture with water and subject it toextraction with ethyl acetate. The organic phase is washed, dried,filtered and concentrated. The residue is freed where appropriate fromany impurities still present by conventional methods, such aschromatography or recrystallization.

Process (B)

A general definition of the Δ¹-pyrrolines required as starting materialswhen carrying out process (B) of the invention is given by the formula(IV). In this formula R¹ and R² stand preferably, with particularpreference or with very particular preference for those definitionswhich have already been mentioned as preferred, particularly preferred,etc. for these radicals in connection with the description of thesubstances of the formula (I) according to the invention. A ispreferably (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or 1,3,2-benzodioxaborol-2-yl,with particular preference(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl or(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl, with very particularpreference (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl.

Δ¹-Pyrrolines of the formula (IV) can be prepared by reacting

-   -   a) compounds of the formula (II)        in which    -   R¹, R² and Z are as defined above with a diboronic ester in the        presence of a catalyst, where appropriate in the presence of an        acid binder and where appropriate in the presence of a diluent        (cf. J. Org. Chem. 1995, 60, 7508; Tetrahedron Lett. 1997, 38,        3447).

Suitable diboronic esters for carrying out process (a) were mentionedabove in connection with the description of process (A) of theinvention.

The heterocycles of the formula (III) required as starting materialswhen carrying out process (B) of the invention have already beendescribed above in connection with the description of process (A).

When carrying out process (B) of the invention generally 1 mol or aslight excess of a compound of the formula (III) is used per mole ofcompound of the formula (V). It is also possible, however, to use thereaction components in other proportions. Working up takes place bycustomary methods. The general procedure is to take up the reactionmixture in ethyl acetate and to wash the organic phase with water, dryit over sodium sulphate, filter it and concentrate the filtrate. Theresidue is where appropriate freed from any impurities that are stillpresent by customary methods, such as chromatography orrecrystallization.

Process (C)

The Δ¹-pyrrolines of the formula (II) required as starting materialswhen carrying out process (C) of the invention have already beendescribed in connection with the description of process (A).

The general definition of the boronic acid derivatives required asstarting materials when carrying out process (C) of the invention isgiven by the formula (V). In this formula Y and R³ stand preferably,with particular preference or with very particular preference for thosedefinitions which have already been mentioned as being preferred,particularly preferred, etc. for these radicals in connection with thedescription of the substances of the formula (I) according to theinvention. A is preferably(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or1,3,2-benzodioxa-borol-2-yl, with particular preference(4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl or(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl, with very particularpreference (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl.

The compounds of the formula (V) are known or can be prepared by knownprocesses (cf. J. Org. Chem. 1995, 60, 7508, Tetrahedron Lett. 1997, 38,3447).

When carrying out process (C) of the invention generally 1 mol or aslight excess of a compound of the formula (V) is used per mole ofcompound of the formula (II). It is also possible, however, to use thereaction components in different proportions. Working up takes place bycustomary methods. The general procedure is to take up the reactionmixture in ethyl acetate and to wash the organic phase with water, dryit over sodium sulphate, filter it and concentrate the filtrate. Theresidue is where appropriate freed from any impurities still present bycustomary methods, such as chromatography or recrystallization.

Process (D)

A general definition of the Δ¹-pyrrolines required as starting materialswhen carrying out process (D) of the invention is given by the formula(II-a). In this formula R¹ and R² stand preferably, with particularpreference or with very particular preference for those definitionswhich have already been mentioned as being preferred, particularlypreferred, etc. for these radicals in connection with the description ofthe substances of the formula (I) according to the invention. Z¹ ispreferably bromine or iodine.

Δ¹-Pyrrolines of the formula (II-a) can be prepared by known processes(cf. WO 98/22438).

A general definition of the organometallic compounds required asstarting materials when carrying out process (D) of the invention isgiven by the formula (VI). In this formula Y and R³ stand preferably,with particular preference or with very particular preference for thosedefinitions which have already been mentioned as being preferred,particularly preferred, etc. for these radicals in connection with thedescription of the substances of the formula (I) according to theinvention. M is preferably ZnCl, Sn(Me)₃ or Sn(n-Bu)₃.

Organometallic compounds of the formula (VI) are known in some cases orcan be prepared by known methods. It is possible, for example, toprepare compounds of the formula (VI) in situ from the correspondingcompounds of the formula (III) in which X is —OSO₂CF₃, (cf. TetrahedronLett. 1995, 36, 9085).

When carrying out process (D) of the invention generally 1 mol or aslight excess of a compound of the formula (VI) is used per mole ofcompound of the formula (II-a). It is also possible, however, to use thereaction components in different proportions. Working up takes place inaccordance with customary methods. The general procedure is to take upthe reaction mixture in ethyl acetate and to wash the organic phase withwater, dry it over sodium sulphate, filter it and concentrate thefiltrate. The residue is freed where appropriate from any impuritiesstill present by customary methods, such as chromatography orrecrystallization.

Chiral Compounds of the Formula (I-a)

Chiral compounds of the formula (I-a) can be prepared, for example, bysubjecting Δ¹-pyrrolines of the formula (II-b)

in which

-   -   R¹ and R² are as defined above and    -   Z² is chlorine, bromine or iodine,    -   to racemate cleavage. This is done by working, for example, in        accordance with methods of preparative chromatography,        preferably by the method of high performance liquid        chromatography (HPLC). A chiral stationary silica gel phase is        used. A silica gel modified with        tris(3,5-dimethylphenylcarbamate)-cellulose has proven to be        particularly suitable for resolving the compounds of the formula        (II-b) into the two enantiomers. This separation material is        available commercially. It is also possible, however, to use        other stationary phases. Suitable mobile phases include all        customary inert, organic solvents, and also mixtures thereof.        Preferred possibilities for use include optionally halogenated        aliphatic, alicyclic or aromatic hydrocarbons, such as petroleum        ether, hexane, heptane, cyclohexane; dichloromethane,        chloroform; alcohols, such as methanol, ethanol, propanol;        nitriles, such as acetonitrile; esters such as methyl acetate or        ethyl acetate. Particular preference is given to using aliphatic        hydrocarbons, such as hexane or heptane, and alcohols, such as        methanol or propanol; very particular preference is given to        n-heptane and isopropanol or mixtures thereof. Operation is        generally carried out at temperatures between 10° C. and 60° C.,        preferably between 10° C. and 40° C., with particular preference        at room temperature. The (R)-configured enantiomers obtained in        this way are then used as starting materials for processes        (A), (C) or (D).

When carrying out processes (A), (B), (C) and (D) of the invention ineach case a palladium catalyst is used which can be employed with orwithout the addition of further ligands. As the catalyst it is preferredto use PdCl₂(dppf) [dppf=1,1′-bis(diphenylphosphino)ferrocene],Pd(PPh₃)₄, PdCl₂(PPh₃)₂, PdCl₂(CH₃CN)₂, Pd₂(dba)₃[dba=dibenzylideneacetone] or Pd(OAc)₂, with particular preferencePdCl₂(dppf), Pd(PPh₃)₄, PdCl₂(PPh₃)₂, or Pd(OAc)₂, with very particularpreference PdCl₂(dppf) or PdCl₂(PPh₃)₂.

Suitable ligands include triarylphosphines, trialkylphosphines orarsines. Preference is given to using dppf, PPh₃, P(tert-Bu)₃, Pcy₃ orAsPh₃, with particular preference dppf.

Suitable diluents when carrying out processes (A), (B) and (C) of theinvention include all customary inert organic solvents. Preferredpossibilities for use are optionally halogenated aliphatic, alicyclic oraromatic hydrocarbons, such as petroleum ether, hexane, heptane,cyclohexane, methylcyclohexane, benzene, toluene, xylene or decalin;chlorobenzene, dichlorobenzene, dichloromethane, chloroform,tetrachloromethane, dichloroethane or trichloroethane; ethers, such asdiethyl ether, diisopropyl ether, methyl tert-butyl ether, methyltert-amyl ether, dioxane, tetrahydrofuran, 1,2-dimethoxyethane,1,2-diethoxyethane or anisole; nitriles, such as acetonitrile,propionitrile, n- or iso-butyronitrile or benzonitrile; amides, such asN,N-dimethylformamide, N,N-dimethylacetamide, N-methyl-formanilide,N-methylpyrrolidone or hexamethylphosphoramide; esters such as methylacetate or ethyl acetate, sulphoxides, such as dimethyl sulphoxide, orsulphones, such as sulpholane. Particular preference is given to usingacetone, di-methoxyethane, dioxane, tetrahydrofuran, dimethylformamide,dimethylacetamide, dimethyl sulphoxide, ethanol, toluene or, whereappropriate, mixtures of these stated diluents with water.

Suitable diluents when carrying out process (D) of the invention includeall customary inert organic solvents. Preferred possibilities for useare optionally halogenated aliphatic, alicyclic or aromatichydrocarbons, such as petroleum ether, hexane, heptane, cyclohexane,methylcyclohexane, benzene, toluene, xylene or decalin; chlorobenzene,dichlorobenzene, dichloromethane, chloroform, tetrachloromethane,dichloroethane or trichloroethane; ethers, such as diethyl ether,diisopropyl ether, methyl tert-butyl ether, methyl tert-amyl ether,dioxane, tetrahydrofuran, 1,2-dimethoxyethane, 1,2-diethoxyethane oranisole. Particular preference is given to using dioxane,tetrahydrofuran or toluene.

Suitable acid binding agents when carrying out the processes (A), (B),(C) and (D) of the invention include in each case all organic andinorganic bases that are customary for such reactions. Preferredpossibilities for use are alkaline earth metal hydroxides or alkalimetal hydroxides, such as sodium hydroxide, calcium hydroxide orpotassium hydroxide, or else ammonium hydroxide, alkali metalcarbonates, such as sodium carbonate, potassium carbonate, potassiumhydrogen carbonate, sodium hydrogen carbonate, alkali metal acetates oralkaline earth metal acetates such as sodium acetate, potassium acetate,calcium acetate, alkali metal fluorides, and also tertiary amines, suchas trimethylamine, triethylamine, tributylamine, N,N-dimethyl-aniline,pyridine, N-methylpiperidine, N,N-dimethylaminopyridine,diazabicyclo-octane (DABCO), diazabicyclononene (DBN) ordiazabicycloundecene (DBU). It is also possible, however, to operatewithout additional acid binder, or to use the amine component in excess,so that it functions simultaneously as an acid binder. Particularpreference is given to using barium hydroxide, sodium hydroxide,potassium hydroxide, tripotassium phosphate, caesium carbonate,potassium carbonate, sodium carbonate, potassium acetate, triethylamine,potassium tert-butoxide, caesium fluoride or potassium fluoride.

The reaction temperatures when carrying out processes (A), (B) and (C)of the invention can in each case be varied within a relatively widerange. They are generally carried out at temperatures between 0° C. and140° C., preferably between 20° C. and 120° C., with particularpreference between 60° C. and 100° C.

The reaction temperatures when carrying out process (D) of the inventioncan in each case be varied within a relatively wide range. It isgenerally carried out at temperatures between 0° C. and 140° C.,preferably between 20° C. and 120° C.,

All processes of the invention are generally carried out underatmospheric pressure. It is also possible, however, to operate underincreased pressure or reduced pressure in each case.

The active compounds are suitable for controlling animal pests, inparticular insects, arachnids and nematodes, which are encountered inagriculture, in forestry, in the protection of stored products and ofmaterials, and in the hygiene sector, and have good plant tolerance andfavourable toxicity to warm-blooded animals. They may be preferablyemployed as plant protection agents. They are active against normallysensitive and resistant species and against all or some stages ofdevelopment. The abovementioned pests include:

-   -   From the order of the Isopoda, for example, Oniscus asellus,        Armadillidium vulgare and Porcellio scaber.    -   From the order of the Diplopoda, for example, Blaniulus        guttulatus.    -   From the order of the Chilopoda, for example, Geophilus        carpophagus and Scutigera spp.    -   From the order of the Symphyla, for example, Scutigerella        immaculata.    -   From the order of the Thysanura, for example, Lepisma        saccharina.    -   From the order of the Collembola, for example, Onychiurus        armatus.    -   From the order of the Orthoptera, for example, Acheta        domesticus, Gryllotalpa spp., Locusta migratoria migratorioides,        Melanoplus spp. and Schistocerca gregaria.    -   From the order of the Blattaria, for example, Blatta orientalis,        Periplaneta americana, Leucophaea maderae and Blattella        germanica.    -   From the order of the Dermaptera, for example, Forficula        auricularia.    -   From the order of the Isoptera, for example, Reticulitermes spp.    -   From the order of the Phthiraptera, for example, Pediculus        humanus corporis, Haematopinus spp., Linognathus spp.,        Trichodectes spp. and Damalinia spp.    -   From the order of the Thysanoptera, for example, Hercinothrips        femoralis, Thrips tabaci, Thrips palmi and Frankliniella        accidentalis.    -   From the order of the Heteroptera, for example, Eurygaster spp.,        Dysdercus intermedius, Piesma quadrata, Cimex lectularius,        Rhodnius prolixus and Triatoma spp.    -   From the order of the Homoptera, for example, Aleurodes        brassicae, Bemisia tabaci, Trialeurodes vaporariorum, Aphis        gossypii, Brevicoryne brassicae, Cryptomyzus ribis, Aphis fabae,        Aphis pomi, Eriosoma lanigerum, Hyalopterus arundinis,        Phylloxera vastatrix, Pemphigus spp., Macrosiphum avenae, Myzus        spp., Phorodon humuli, Rhopalosiphum padi, Empoasca spp.,        Euscelis bilobatus, Nephotettix cincticeps, Lecanium corni,        Saissetia oleae, Laodelphax striatellus, Nilaparvata lugens,        Aonidiella aurantii, Aspidiotus hederae, Pseudococcus spp. and        Psylla spp.    -   From the order of the Lepidoptera, for example, Pectinophora        gossypiella, Bupalus piniarius, Cheimatobia brumata,        Lithocolletis blancardella, Hyponomeuta padella, Plutella        xylostella, Malacosoma neustria, Euproctis chrysorrhoea,        Lymantria spp., Bucculatrix thurberiella, Phyllocnistis        citrella, Agrotis spp., Euxoa spp., Feltia spp., Earias        insulana, Heliothis spp., Mamestra brassicae, Panolis flammea,        Spodoptera spp., Trichoplusia ni, Carpocapsa pomonella, Pieris        spp., Chilo spp., Pyrausta nubilalis, Ephestia kuehniella,        Galleria mellonella, Tineola bisselliella, Tinea pellionella,        Hoffmannophila pseudospretella, Cacoecia podana, Capua        reticulana, Choristoneura fumiferana, Clysia ambiguella, Homona        magnanima, Tortrix viridana, Cnaphalocerus spp., Oulema oryzae.    -   From the order of the Coleoptera, for example, Anobium        punctatum, Rhizopertha dominica, Bruchidius obtectus,        Acanthoscelides obtectus, Hylotrupes bajulus, Agelastica alni,        Leptinotarsa decemlineata, Phaedon cochleariae, Diabrotica spp.,        Psylliodes chrysocephala, Epilachna varivestis, Atomaria spp.,        Oryzaephilus surinamensis, Anthonomus spp., Sitophilus spp.,        Otiorrhynchus sulcatus, Cosmopolites sordidus, Ceuthorrhynchus        assimilis, Hypera postica, Dermestes spp., Trogoderma spp.,        Anthrenus spp., Attagenus spp., Lyctus spp., Meligethes aeneus,        Ptinus spp., Niptus hololeucus, Gibbium psylloides, Tribolium        spp., Tenebrio molitor, Agriotes spp., Conoderus spp.,        Melolontha melolontha, Amphimallon solstitialis, Costelytra        zealandica and Lissorhoptrus oryzophilus.    -   From the order of the Hymenoptera, for example, Diprion spp.,        Hoplocampa spp., Lasius spp., Monomorium pharaonis and Vespa        spp.    -   From the order of the Diptera, for example, Aedes spp.,        Anopheles spp., Culex spp., Drosophila melanogaster, Musca spp.,        Fannia spp., Calliphora erythrocephala, Lucilia spp., Chrysomyia        spp., Cuterebra spp., Gastrophilus spp., Hyppobosca spp.,        Stomoxys spp., Oestrus spp., Hypoderma spp., Tabanus spp.,        Tannia spp., Bibio hortulanus, Oscinella frit, Phorbia spp.,        Pegomyia hyoscyami, Ceratitis capitata, Dacus oleae, Tipula        paludosa, Hylemyia spp. and Liriomyza spp.    -   From the order of the Siphonaptera, for example, Xenopsylla        cheopis and Ceratophyllus spp.    -   From the class of the Arachnida, for example, Scorpio maurus,        Latrodectus mactans, Acarus siro, Argas spp., Ornithodoros spp.,        Dermanyssus gallinae, Eriophyes ribis, Phyllocoptruta oleivora,        Boophilus spp., Rhipicephalus spp., Amblyomma spp., Hyalomma        spp., Ixodes spp., Psoroptes spp., Chorioptes spp., Sarcoptes        spp., Tarsonemus spp., Bryobia praetiosa, Panonychus spp.,        Tetranychus spp., Hemitarsonemus spp., Brevipalpus spp.

The phytoparasitic nematodes include, for example, Pratylenchus spp.,Radopholus similis, Ditylenchus dipsaci, Tylenchulus semipenetrans,Heterodera spp., Globodera spp., Meloidogyne spp., Aphelenchoides spp.,Longidorus spp., Xiphinema spp., Trichodorus spp., Bursaphelenchus spp.

In particular, the compounds of the formula (I) according to theinvention have excellent activity against caterpillars, beetle larvae,spider mites, aphids and leaf-mining flies.

The substances of the invention additionally display a very goodduration of action, such as against the caterpillars of the cottonbudworm (Heliothis virescens) or the caterpillars of the armyworm(Spodoptera frugiperda).

If appropriate, the compounds according to the invention can, at certainconcentrations or application rates, also be used as herbicides ormicrobicides, for example as fungicides, antimycotics and bactericides.If appropriate, they can also be employed as intermediates or precursorsfor the synthesis of other active compounds.

All plants and plant parts can be treated in accordance with theinvention. Plants are to be understood as meaning in the present contextall plants and plant populations such as desired and undesired wildplants or crop plants (including naturally occurring crop plants). Cropplants can be plants which can be obtained by conventional plantbreeding and optimization methods or by biotechnological and recombinantmethods or by combinations of these methods, including the transgenicplants and including the plant cultivars protectable or not protectableby plant breeders' rights. Plant parts are to be understood as meaningall parts and organs of plants above and below the ground, such asshoot, leaf, flower and root, examples which may be mentioned beingleaves, needles, stalks, stems, flowers, fruit bodies, fruits, seeds,roots, tubers and rhizomes. The plant parts also include harvestedmaterial, and vegetative and generative propagation material, forexample cuttings, tubers, rhizomes, offsets and seeds.

Treatment according to the invention of the plants and plant parts withthe active compounds is carried out directly or by allowing thecompounds to act on their surroundings, environment or storage space bythe customary treatment methods, for example by immersion, spraying,evaporation, fogging, scattering, painting on and, in the case ofpropagation material, in particular in the case of seeds, also byapplying one or more coats.

The active compounds according to the invention can be converted intothe customary formulations, such as solutions, emulsions, wettablepowders, suspensions, powders, dusts, pastes, soluble powders, granules,suspension-emulsion concentrates, natural and synthetic materialsimpregnated with active compound and microencapsulations in polymericsubstances.

These formulations are produced in a known manner, for example by mixingthe active compounds according to the invention with extenders, that isliquid solvents and/or solid carriers, optionally with the use ofsurfactants, that is emulsifiers and/or dispersants and/or foam-formers.

If the extender used is water, it is also possible to employ for exampleorganic solvents as auxiliary solvents. Essentially, suitable liquidsolvents are: aromatics such as xylene, toluene or alkylnaphthalenes,chlorinated aromatics and chlorinated aliphatic hydrocarbons such aschlorobenzenes, chloroethylenes or methylene chloride, aliphatichydrocarbons such as cyclohexane or paraffins, for example petroleumfractions, mineral and vegetable oils, alcohols such as butanol orglycol and also their ethers and esters, ketones such as acetone, methylethyl ketone, methyl isobutyl ketone or cyclohexanone, strongly polarsolvents such as dimethylformamide and dimethyl sulphoxide, and alsowater.

Suitable solid carriers are:

-   -   for example ammonium salts and ground natural minerals such as        kaolins, clays, talc, chalk, quartz, attapulgite,        montmorillonite or diatomaceous earth, and ground synthetic        minerals, such as highly disperse silica, alumina and silicates;        suitable solid carriers for granules are: for example crushed        and fractionated natural rocks such as calcite, marble, pumice,        sepiolite and dolomite, and also synthetic granules of inorganic        and organic meals, and granules of organic material such as        sawdust, coconut shells, maize cobs and tobacco stalks; suitable        emulsifiers and/or foam-formers are: for example nonionic and        anionic emulsifiers, such as polyoxyethylene fatty acid esters,        polyoxyethylene fatty alcohol ethers, for example alkylaryl        polyglycol ethers, alkylsulphonates, alkyl sulphates,        arylsulphonates and also protein hydrolysates; suitable        dispersants are: for example lignosulphite waste liquors and        methylcellulose.    -   Tackifiers such as carboxymethylcellulose and natural and        synthetic polymers in the form of powders, granules or latices,        such as gum arabic, polyvinyl alcohol and polyvinyl acetate, as        well as natural phospholipids such as cephalins and lecithins,        and synthetic phospholipids, can be used in the formulations.        Other additives can be mineral and vegetable oils.

It is possible to use colorants such as inorganic pigments, for exampleiron oxide, titanium oxide and Prussian Blue, and organic dyestuffs,such as alizarin dyestuffs, azo dyestuffs and metal phthalocyaninedyestuffs, and trace nutrients such as salts of iron, manganese, boron,copper, cobalt, molybdenum and zinc.

The formulations generally comprise between 0.1 and 95% by weight ofactive compound, preferably between 0.5 and 90%.

The active compounds according to the invention can be used as such orin their formulations as a mixture with known fungicides, bactericides,acaracides, nematicides or insecticides, in order, for example, toincrease the spectrum of activity or to prevent the development ofresistance. In many cases synergistic effects are thus achieved, ie theefficacy of the mixture is greater than the efficacy of the individualcomponents.

Particularly advantageous co-components are, for example, the following:

Fungicides:

-   -   aldimorph, ampropylfos, ampropylfos-potassium, andoprim,        anilazine, azaconazole, azoxystrobin,    -   benalaxyl, benodanil, benomyl, benzamacril,        benzamacryl-isobutyl, bialaphos, binapacryl, biphenyl,        bitertanol, blasticidin-S, bromuconazole, bupirimate,        buthiobate, calcium polysulphide, carpropamide, capsimycin,        captafol, captan, carbendazim, carboxin, carvon,        quinomethionate, chlobenthiazone, chlorfenazole, chloroneb,        chloropicrin, chlorothalonil, chlozolinate, clozylacon,        cufraneb, cymoxanil, cyproconazole, cyprodinil, cyprofuram,    -   debacarb, dichlorophen, diclobutrazole, diclofluanid,        diclomezine, dicloran, diethofencarb, difenoconazole,        dimethirimol, dimethomorph, diniconazole, diniconazole-M,        dinocap, diphenylamine, dipyrithione, ditalimfos, dithianon,        dodemorph, dodine, drazoxolon,    -   edifenphos, epoxiconazole, etaconazole, ethirimol, etridiazole,    -   famoxadon, fenapanil, fenarimol, fenbuconazole, fenfuram,        fenhexamide, fenitropan, fenpiclonil, fenpropidin,        fenpropimorph, fentin acetate, fentin hydroxide, ferbam,        ferimzone, fluazinam, flumetover, fluoromide, fluquinconazole,        flurprimidol, flusilazole, flusulphamide, flutolanil,        flutriafol, folpet, fosetyl-aluminium, fosetyl-sodium, fthalide,        fuberidazole, furalaxyl, furametpyr, furcarbonil, furconazole,        furconazole-cis, furmecyclox, guazatine, hexachlorobenzene,        hexaconazole, hymexazole,    -   imazalil, imibenconazole, iminoctadine, iminoctadine albesilate,        iminoctadine triacetate, iodocarb, ipconazole, iprobenfos (IBP),        iprodione, iprovalicarb, irumamycin, isoprothiolane,        isovaledione,    -   kasugamycin, kresoxim-methyl, copper preparations, such as:        copper hydroxide, copper naphthenate, copper oxychloride, copper        sulphate, copper oxide, oxine-copper and Bordeaux mixture,    -   mancopper, mancozeb, maneb, meferimzone, mepanipyrim, mepronil,        metalaxyl, metconazole, methasulfocarb, methfuroxam, metiram,        metomeclam, metsulfovax, mildiomycin, myclobutanil, myclozolin,    -   nickel dimethyldithiocarbamate, nitrothal-isopropyl, nuarimol,    -   ofurace, oxadixyl, oxamocarb, oxolinic acid, oxycarboxim,        oxyfenthiin,    -   paclobutrazole, pefurazoate, penconazole, pencycuron,        phosdiphen, picoxystrobin, pimaricin, piperalin, polyoxin,        polyoxorim, probenazole, prochloraz, procymidone, propamocarb,        propanosine-sodium, propiconazole, propineb, pyraclostrobin,        pyrazophos, pyrifenox, pyrimethanil, pyroquilon, pyroxyfur,    -   quinconazole, quintozene (PCNB), quinoxyfen,    -   sulphur and sulphur preparations, spiroxamine,    -   tebuconazole, tecloftalam, tecnazene, tetcyclacis,        tetraconazole, thiabendazole, thicyofen, thifluzamide,        thiophanate-methyl, thiram, tioxymid, tolclofos-methyl,        tolylfluanid, triadimefon, triadimenol, triazbutil, triazoxide,        trichlamide, tricyclazole, tridemorph, trifloxystrobin,        triflumizole, triforine, triticonazole,    -   uniconazole,    -   validamycin A, vinclozolin, viniconazole,    -   zarilamide, zineb, ziram and also    -   Dagger G, OK-8705, OK-8801,    -   α-(1,1-dimethylethyl)-β-(2-phenoxyethyl)-1H-1,2,4-triazole-1-ethanol,    -   α-(2,4-dichlorophenyl)-β-fluoro-β-propyl-1H-1,2,4-triazole-1-ethanol,    -   α-(2,4-dichlorophenyl)-β-methoxy-α-methyl-1H-1,2,4-triazole-1-ethanol,    -   α-(5-methyl-1,3-dioxan-5-yl)-β-[[4-(trifluoromethyl)-phenyl]-methylene]-1H-1,2,4-triazole-1-ethanol,    -   (5RS,6RS)-6-hydroxy-2,2,7,7-tetramethyl-5-(1H-1,2,4-triazol-1-yl)-3-octanone,    -   (E)-α-(methoxyimino)-N-methyl-2-phenoxy-phenylacetamide,    -   1-(2,4-dichlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-ethanone-O-(phenylmethyl)-oxime,    -   1-(2-methyl-1-naphthalenyl)-1H-pyrrole-2,5-dione,    -   1-(3,5-dichlorophenyl)-3-(2-propenyl)-2,5-pyrrolidinedione,    -   1-[(diiodomethyl)-sulphonyl]-4-methyl-benzene,    -   1-[[2-(2,4-dichlorophenyl)-1,3-dioxolan-2-yl]-methyl]-1H-imidazole,    -   1-[[2-(4-chlorophenyl)-3-phenyloxiranyl]-methyl]-1H-1,2,4-triazole,    -   1-[1-[2-[(2,4-dichlorophenyl)-methoxy]-phenyl]-ethenyl]-1H-imidazole,    -   1-methyl-5-nonyl-2-(phenylmethyl)-3-pyrrolidinole,    -   2′,6′-dibromo-2-methyl-4′-trifluoromethoxy-4′-trifluoro-methyl-1,3-thiazole-5-carboxanilide,    -   2,6-dichloro-5-(methylthio)-4-pyrimidinyl-thiocyanate,    -   2,6-dichloro-N-(4-trifluoromethylbenzyl)-benzamide,    -   2,6-dichloro-N-[[4-(trifluoromethyl)-phenyl]-methyl]-benzamide,    -   2-(2,3,3-triiodo-2-propenyl)-2H-tetrazole,    -   2-[(1-methylethyl)-sulphonyl]-5-(trichloromethyl)-1,3,4-thiadiazole,    -   2-[[6-deoxy-4-O-(4-O-methyl-β-D-glycopyranosyl)-α-D-glucopyranosyl]-amino]-4-methoxy-1H-pyrrolo[2,3-d]pyrimidine-5-carbonitrile,    -   2-aminobutane,    -   2-bromo-2-(bromomethyl)-pentanedinitrile,    -   2-chloro-N-(2,3-dihydro-1,1,3-trimethyl-1H-inden-4-yl)-3-pyridinecarboxamide,    -   2-chloro-N-(2,6-dimethylphenyl)-N-(isothiocyanatomethyl)-acetamide,    -   2-phenylphenol (OPP),    -   3,4-dichloro-1-[4-(difluoromethoxy)-phenyl]-1H-pyrrole-2,5-dione,    -   3,5-dichloro-N-[cyano[(1-methyl-2-propynyl)-oxy]-methyl]-benzamide,    -   3-(1,1-dimethylpropyl-1-oxo-1H-indene-2-carbonitrile,    -   3-[2-(4-chlorophenyl)-5-ethoxy-3-isoxazolidinyl]-pyridine,    -   4-chloro-2-cyano-N,N-dimethyl-5-(4-methylphenyl)-1H-imidazole-1-sulphonamide,    -   4-methyl-tetrazolo[1,5-a]quinazolin-5(4H)-one,    -   8-hydroxyquinoline sulphate,    -   9H-xanthene-2-[(phenylamino)-carbonyl]-9-carboxylic hydrazide,    -   bis-(1-methylethyl)-3-methyl-4-[(3-methylbenzoyl)-oxy]-2,5-thiophenedicarboxylate,    -   cis-1-(4-chlorophenyl)-2-(1H-1,2,4-triazol-1-yl)-cycloheptanol,    -   cis-4-[3-[4-(1,1-dimethylpropyl)-phenyl-2-methylpropyl]-2,6-dimethyl-morpholine        hydrochloride,    -   ethyl [(4-chlorophenyl)-azo]-cyanoacetate,    -   potassium bicarbonate,    -   methanetetrathiol-sodium salt,    -   methyl        1-(2,3-dihydro-2,2-dimethyl-1H-inden-1-yl)-1H-imidazole-5-carboxylate,    -   methyl        N-(2,6-dimethylphenyl)-N-(5-isoxazolylcarbonyl)-DL-alaninate,    -   methyl N-(chloroacetyl)-N-(2,6-dimethylphenyl)-DL-alaninate,    -   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-furanyl)-acetamide,    -   N-(2,6-dimethylphenyl)-2-methoxy-N-(tetrahydro-2-oxo-3-thienyl)-acetamide,    -   N-(2-chloro-4-nitrophenyl)-4-methyl-3-nitro-benzenesulphonamide,    -   N-(4-cyclohexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,    -   N-(4-hexylphenyl)-1,4,5,6-tetrahydro-2-pyrimidinamine,    -   N-(5-chloro-2-methylphenyl)-2-methoxy-N-(2-oxo-3-oxazolidinyl)-acetamide,    -   N-(6-methoxy-3-pyridinyl)-cyclopropanecarboxamide,    -   N-[2,2,2-trichloro-1-[(chloroacetyl)-amino]-ethyl]-benzamide,    -   N-[3-chloro-4,5-bis(2-propinyloxy)-phenyl]-N′-methoxy-methanimidamide,    -   N-formyl-N-hydroxy-DL-alanine-sodium salt,    -   O,O-diethyl[2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate,    -   O-methyl S-phenyl phenylpropylphosphoramidothioate,    -   S-methyl 1,2,3-benzothiadiazole-7-carbothioate,    -   spiro[2H]-1-benzopyran-2,1′(3′H)-isobenzofuran-3′-one,    -   4-[3,4-dimethoxyphenyl)-3-(4-fluorophenyl)-acryloyl]-morpholine        Bactericides:

bronopol, dichlorophen, nitrapyrin, nickel dimethyldithiocarbamate,kasugamycin, octhilinone, furancarboxylic acid, oxytetracyclin,probenazole, streptomycin, tecloftalam, copper sulphate and other copperpreparations.

Insecticides/Acaricides/Nematicides:

-   -   abamectin, acephate, acetamiprid, acrinathrin, alanycarb,        aldicarb, aldoxycarb, alpha-cypernethrin, alphamethrin, amitraz,        avermectin, AZ 60541, azadirachtin, azamethiphos, azinphos A,        azinphos M, azocyclotin,    -   Bacillus popilliae, Bacillus sphaericus, Bacillus subtilis,        Bacillus thuringiensis, baculoviruses, Beauveria bassiana,        Beauveria tenella, bendiocarb, benfuracarb, bensultap,        benzoximate, betacyfluthrin, bifenazate, bifenthrin,        bioethanomethrin, biopermethrin, bistrifluron, BPMC, bromophos        A, bufencarb, buprofezin, butathiofos, butocarboxim,        butylpyridaben,    -   cadusafos, carbaryl, carbofuran, carbophenothion, carbosulphan,        cartap, chloethocarb, chlorethoxyfos, chlorfenapyr,        chlorfenvinphos, chlorfluazuron, chlormephos, chlorpyrifos,        chlorpyrifos M, chlovaporthrin, chromafenozide, cis-resmethrin,        cispermethrin, clocythrin, cloethocarb, clofentezine,        clothianidine, cyanophos, cycloprene, cycloprothrin, cyfluthrin,        cyhalothrin, cyhexatin, cypermethrin, cyromazine,    -   deltamethrin, demeton M, demeton S, demeton-S-methyl,        diafenthiuron, diazinon, dichlorvos, dicofol, diflubenzuron,        dimethoate, dimethylvinphos, diofenolan, disulfoton,        docusat-sodium, dofenapyn,    -   eflusilanate, emamectin, empenthrin, endosulfan, Entomopfthora        spp., esfenvalerate, ethiofencarb, ethion, ethoprophos,        etofenprox, etoxazole, etrimfos,    -   fenamiphos, fenazaquin, fenbutatin oxide, fenitrothion,        fenothiocarb, fenoxacrim, fenoxycarb, fenpropathrin, fenpyrad,        fenpyrithrin, fenpyroximate, fenvalerate, fipronil, fluazuron,        flubrocythrinate, flucycloxuron, flucythrinate, flufenoxuron,        flumethrin, flutenzine, fluvalinate, fonophos, fosmethilan,        fosthiazate, fubfenprox, furathiocarb,    -   granulosis viruses,    -   halofenozide, HCH, heptenophos, hexaflumuron, hexythiazox,        hydroprene,    -   imidacloprid, indoxacarb, isazofos, isofenphos, isoxathion,        ivermectin,    -   nuclear polyhedrosis viruses,    -   lambda-cyhalothrin, lufenuron,    -   malathion, mecarbam, metaldehyde, methamidophos, Metharhizium        anisopliae, Metharhizium flavoviride, methidathion, methiocarb,        methoprene, methomyl, methoxyfenozide, metolcarb, metoxadiazone,        mevinphos, milbemectin, milbemycin, monocrotophos,    -   naled, nitenpyram, nithiazine, novaluron,    -   omethoate, oxamyl, oxydemethon M,    -   Paecilomyces fumosoroseus, parathion A, parathion M, permethrin,        phenthoate, phorate, phosalone, phosmet, phosphamidon, phoxim,        pirimicarb, pirimiphos A, pirimiphos M, profenofos, promecarb,        propargite, propoxur, prothiofos, prothoate, pymetrozine,        pyraclofos, pyresmethrin, pyrethrum, pyridaben, pyridathion,        pyrimidifen, pyriproxyfen,    -   quinalphos,    -   ribavirin,    -   salithion, sebufos, silafluofen, spinosad, spirodiclofen,        sulphotep, sulprofos,    -   tau-fluvalinate, tebufenozide, tebufenpyrad, tebupirimiphos,        teflubenzuron, tefluthrin, temephos, temivinphos, terbufos,        tetrachlorvinphos, tetradifon, theta-cypermethrin, thiacloprid,        thiamethoxam, thiapronil, thiatriphos, thiocyclam hydrogen        oxalate, thiodicarb, thiofanox, thuringiensin, tralocythrin,        tralomethrin, triarathene, triazamate, triazophos, triazuron,        trichlophenidine, trichlorfon, triflumuron, trimethacarb,    -   vamidothion, vaniliprole, Verticillium lecanii,    -   YI 5302,    -   zeta-cypermethrin, zolaprofos,    -   (1R-cis)-[5-(phenylmethyl)-3-furanyl]-methyl-3-[(dihydro-2-oxo-3(2H)-furanylidene)-methyl]-2,2-dimethylcyclopropanecarboxylate,    -   (3-phenoxyphenyl)-methyl-2,2,3,3-tetramethylcyclopropanecarboxylate,    -   1-[(2-chloro-5-thiazolyl)methyl]tetrahydro-3,5-dimethyl-N-nitro-1,3,5-triazine-2(1H)-imine,    -   2-(2-chloro-6-fluorophenyl)-4-[4-(1,1-dimethylethyl)phenyl]-4,5-dihydro-oxazole,    -   2-(acetyloxy)-3-dodecyl-1,4-naphthalenedione,    -   2-chloro-N-[[[4-(1-phenylethoxy)-phenyl]-amino]-carbonyl]-benzamide,    -   2-chloro-N-[[[4-(2,2-dichloro-1,1-difluoroethoxy)-phenyl]-amino]-carbonyl]-benzamide,    -   3-methylphenyl propylcarbamate.    -   4-[4-(4-ethoxyphenyl)-4-methylpentyl]-1-fluoro-2-phenoxy-benzene,    -   4-chloro-2-(1,1-dimethylethyl)-5-[[2-(2,6-dimethyl-4-phenoxyphenoxy)ethyl]thio]-3(2H)-pyridazinone,    -   4-chloro-2-(2-chloro-2-methylpropyl)-5-[(6-iodo-3-pyridinyl)methoxy]-3(2H)-pyridazinone,    -   4-chloro-5-[(6-chloro-3-pyridinyl)methoxy]-2-(3,4-dichlorophenyl)-3(2H)-pyridazinone,    -   Bacillus thuringiensis strain EG-2348,    -   [2-benzoyl-1-(1,1-dimethylethyl)-hydrazinobenzoic acid,    -   2,2-dimethyl-3-(2,4-dichlorophenyl)-2-oxo-1-oxaspiro[4.5]dec-3-en-4-yl        butanoate,    -   [3-[(6-chloro-3-pyridinyl)methyl]-2-thiazolidinylidene]-cyanamide,    -   dihydro-2-(nitromethylene)-2H-1,3-thiazine-3(4H)-carboxaldehyde,    -   ethyl        [2-[[1,6-dihydro-6-oxo-1-(phenylmethyl)-4-pyridazinyl]oxy]ethyl]-carbamate,    -   N-(3,4,4-trifluoro-1-oxo-3-butenyl)-glycine,    -   N-(4-chlorophenyl)-3-[4-(difluoromethoxy)phenyl]-4,5-dihydro-4-phenyl-1H-pyrazole-1-carboxamide,    -   N-[(2-chloro-5-thiazolyl)methyl]-N ′-methyl-N″-nitro-guanidine,    -   N-methyl-N′-(1-methyl-2-propenyl)-1,2-hydrazinedicarbothioamide,    -   N-methyl-N′-2-propenyl-1,2-hydrazinedicarbothioamide,    -   O,O-diethyl        [2-(dipropylamino)-2-oxoethyl]-ethylphosphoramidothioate    -   N-cyanomethyl-4-trifluoromethyl-nicotinamide    -   3,5-dichloro-1-(3,3-dichloro-2-propenyloxy)-4-[3-(5-trifluoromethylpyridin-2-yloxy)-propoxy]-benzene

It is also possible to admix other known active compounds, such asherbicides, fertilizers and growth regulators.

When used as insecticides, the active compounds according to theinvention can furthermore be present in their commercially availableformulations and in the use forms, prepared from these formulations, asa mixture with synergistic agents. Synergistic agents are compoundswhich increase the action of the active compounds according to theinvention, without it being necessary for the synergistic agent added tobe active itself.

The active compound content of the use forms prepared from thecommercially available formulations can vary within wide limits. Theactive compound concentration of the use forms can be from 0.0000001 to95% by weight of active compound, preferably between 0.0001 and 1% byweight.

The compounds are employed in a customary manner appropriate for the useforms.

When used against hygiene pests and pests of stored products, the activecompound is distinguished by an excellent residual action on wood andclay as well as a good stability to alkali on limed substrates.

As already mentioned above, it is possible to treat all plants and theirparts according to the invention. In a preferred embodiment, wild plantspecies and plant cultivars, or those obtained by conventionalbiological breeding, such as crossing or protoplast fusion, and partsthereof, are treated. In a further preferred embodiment, transgenicplants and plant cultivars obtained by genetic engineering, ifappropriate in combination with conventional methods (GeneticallyModified Organisms), and parts thereof are treated. The term “parts” or“parts of plants” or “plant parts” has been explained above.

Particularly preferably, plants of the plant cultivars which are in eachcase commercially available or in use are treated according to theinvention. By plant cultivars are meant plants having new properties(“traits”), bred either by conventional breeding, by mutagenesis or byrecombinant DNA techniques. They may be cultivars, biotypes andgenotypes.

Depending on the plant species or plant cultivars, their location andgrowth conditions (soils, climate, vegetation period, diet), thetreatment according to the invention may also result in superadditive(“synergistic”) effects. Thus, for example, reduced application ratesand/or a widening of the activity spectrum and/or an increase in theactivity of the substances and compositions to be used according to theinvention, better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products are possible whichexceed the effects which were actually to be expected.

The preferred transgenic plants or plant cultivars (i.e. those obtainedby genetic engineering) which are to be treated according to theinvention include all plants which, in the genetic modification,received genetic material which imparted particularly advantageoususeful properties (“traits”) to these plants. Examples of suchproperties are better plant growth, increased tolerance to high or lowtemperatures, increased tolerance to drought or to water or soil saltcontent, increased flowering performance, easier harvesting, acceleratedmaturation, higher harvest yields, better quality and/or a highernutritional value of the harvested products, better storage stabilityand/or processability of the harvested products. Further andparticularly emphasized examples of such properties are a better defenceof the plants against animal and microbial pests, such as againstinsects, mites, phytopathogenic fungi, bacteria and/or viruses, and alsoincreased tolerance of the plants to certain herbicidally activecompounds. Examples of transgenic plants which may be mentioned are theimportant crop plants, such as cereals (wheat, rice), maize, soya beans,potatoes, cotton, oilseed rape and also fruit plants (with the fruitsapples, pears, citrus fruits and grapevines), and particular emphasis isgiven to maize, soya beans, potatoes, cotton and oilseed rape. Traitsthat are emphasized are in particular increased defence of the plantsagainst insects by toxins formed in the plants, in particular thoseformed by the genetic material from Bacillus thuringiensis (for exampleby the genes CryIA(a), CryIA(b), CryIA(c), CryIIA, CryIIIA, CryIIIB2,Cry9c, Cry2Ab, Cry3Bb and CryIF and also combinations thereof)(hereinbelow referred to as “Bt plants”). Traits that are alsoparticularly emphasized are increased defence of plants against fungi,bacteria and viruses by systematic acquired resistance (SAR), systemine,phytoalexins, elicitors and resistance genes and corresponding expressedproteins and toxins. Traits that are furthermore particularly emphasizedare the increased tolerance of the plants to certain herbicidally activecompounds, for example imidazolinones, sulphonylureas, glyphosate orphosphinotricin (for example the “PAT” gene). The genes which impart thedesired traits in question can also be present in combination with oneanother in the transgenic plants. Examples of “Bt plants” which may bementioned are maize varieties, cotton varieties, soya bean varieties andpotato varieties which are sold under the trade names YIELD GARD® (forexample maize, cotton, soya beans), KnockOut® (for example maize),StarLink® (for example maize), Bollgard® (cotton), Nucotn® (cotton) andNewLeaf® (potato). Examples of herbicide-tolerant plants which may bementioned are maize varieties, cotton varieties and soya bean varietieswhich are sold under the trade names Roundup Ready® (tolerance toglyphosate, for example maize, cotton, soya bean), Liberty Link®(tolerance to phosphinotricin, for example oilseed rape), IMI®(tolerance to imidazolinones) and STS® (tolerance to sulphonylureas, forexample maize). Herbicide-resistant plants (plants bred in aconventional manner for herbicide tolerance) which may be mentionedinclude the varieties sold under the name Clearfield® (for examplemaize). Of course, these statements also apply to plant cultivars havingthese or still to be developed genetic traits, which plants will bedeveloped and/or marketed in the future.

The plants listed can be treated according to the invention in aparticularly advantageous manner with the compounds of the generalformula (I) or the active compound mixtures according to the invention.The preferred ranges stated above for the active compounds or mixturesalso apply to the treatment of these plants. Particular emphasis isgiven to the treatment of plants with the compounds or the mixturesspecifically mentioned in the present text.

The active compounds according to the invention act not only againstplant, hygiene and stored product pests, but also in the veterinarymedicine sector against animal parasites (ectoparasites), such as hardticks, soft ticks, mange mites, leaf mites, flies (biting and licking),parasitic fly larvae, lice, hair lice, feather lice and fleas. Theseparasites include:

-   -   From the order of the Anoplurida, for example, Haematopinus        spp., Linognathus spp., Pediculus spp., Phtirus spp. and        Solenopotes spp.    -   From the order of the Mallophagida and the suborders Amblycerina        and Ischnocerina, for example, Trimenopon spp., Menopon spp.,        Trinoton spp., Bovicola spp., Wemeckiella spp., Lepikentron        spp., Damalina spp., Trichodectes spp. and Felicola spp.    -   From the order of the Diptera and the suborders Nematocerina and        Brachycerina, for example, Aedes spp., Anopheles spp., Culex        spp., Simulium spp., Eusimulium spp., Phlebotomus spp.,        Lutzomyia spp., Culicoides spp., Chrysops spp., Hybomitra spp.,        Atylotus spp., Tabanus spp., Haematopota spp., Philipomyia spp.,        Braula spp., Musca spp., Hydrotaea spp., Stomoxys spp.,        Haematobia spp., Morellia spp., Fannia spp., Glossina spp.,        Calliphora spp., Lucilia spp., Chrysomyia spp., Wohlfahrtia        spp., Sarcophaga spp., Oestrus spp., Hypoderma spp.,        Gasterophilus spp., Hippobosca spp., Lipoptena spp. and        Melophagus spp.    -   From the order of the Siphonapterida, for example, Pulex spp.,        Ctenocephalides spp., Xenopsylla spp. and Ceratophyllus spp.    -   From the order of the Heteropterida, for example, Cimex spp.,        Triatoma spp., Rhodnius spp. and Panstrongylus spp.    -   From the order of the Blattarida, for example, Blatta        orientalis, Periplaneta americana, Blattella germanica and        Supella spp.    -   From the subclass of the Acaria (Acarida) and the orders of the        Meta- and Mesostigmata, for example, Argas spp., Ornithodorus        spp., Otobius spp., Ixodes spp., Amblyomma spp., Boophilus spp.,        Dermacentor spp., Haemophysalis spp., Hyalomma spp.,        Rhipicephalus spp., Dermanyssus spp., Raillietia spp.,        Pneumonyssus spp., Stemostoma spp. and Varroa spp.    -   From the order of the Actinedida (Prostigmata) und Acaridida        (Astigmata), for example, Acarapis spp., Cheyletiella spp.,        Ornithocheyletia spp., Myobia spp., Psorergates spp., Demodex        spp., Trombicula spp., Listrophorus spp., Acarus spp.,        Tyrophagus spp., Caloglyphus spp., Hypodectes spp., Pterolichus        spp., Psoroptes spp., Chorioptes spp., Otodectes spp., Sarcoptes        spp., Notoedres spp., Knemidocoptes spp., Cytodites spp. and        Laminosioptes spp.

The active compounds of the formula (I) according to the invention arealso suitable for controlling arthropods which infest agriculturalproductive livestock, such as, for example, cattle, sheep, goats,horses, pigs, donkeys, camels, buffalo, rabbits, chickens, turkeys,ducks, geese and bees, other pets, such as, for example, dogs, cats,caged birds and aquarium fish, and also so-called test animals, such as,for example, hamsters, guinea pigs, rats and mice. By controlling thesearthropods, cases of death and reduction in productivity (for meat,milk, wool, hides, eggs, honey etc.) should be diminished, so that moreeconomic and easier animal husbandry is possible by use of the activecompounds according to the invention.

The active compounds according to the invention are used in theveterinary sector in a known manner by enteral administration in theform of, for example, tablets, capsules, potions, drenches, granules,pastes, boluses, the feed-through process and suppositories, byparenteral administration, such as, for example, by injection(intramuscular, subcutaneous, intravenous, intraperitoneal and thelike), implants, by nasal administration, by dermal use in the form, forexample, of dipping or bathing, spraying, pouring on and spotting on,washing and powdering, and also with the aid of moulded articlescontaining the active compound, such as collars, ear marks, tail marks,limb bands, halters, marking devices and the like.

When used for cattle, poultry, pets and the like, the active compoundsof the formula (I) according to the invention can be used asformulations (for example powders, emulsions, free-flowingcompositions), which comprise the active compounds according to theinvention in an amount of 1 to 80% by weight, directly or after 100 to10 000-fold dilution, or they can be used as a chemical bath.

It has furthermore been found that the compounds according to theinvention have a strong insecticidal action against insects whichdestroy industrial materials.

The following insects may be mentioned as examples and as preferred—butwithout a limitation:

-   -   Beetles, such as    -   Hylotrupes bajulus, Chlorophorus pilosis, Anobium punctatum,        Xestobium rufovillosum, Ptilinus pecticonis, Dendrobium        pertinex, Emobius mollis, Priobium carpini, Lyctus brunneus,        Lyctus africanus, Lyctus planicollis, Lyctus linearis, Lyctus        pubescens, Trogoxylon aequale, Minthes rugicollis, Xyleborus        spec., Tryptodendron spec., Apate monachus, Bostrychus capucins,        Heterobostrychus brunneus, Sinoxylon spec., Dinoderus minutus.    -   Hymenopterons, such as    -   Sirex juvencus, Urocerus gigas, Urocerus gigas taignus, Urocerus        augur.    -   Termites, such as    -   Kalotermes flavicollis, Cryptotermes brevis, Heterotermes        indicola, Reticulitermes flavipes, Reticulitermes santonensis,        Reticulitermes lucifugus, Mastotermes darwiniensis, Zootennopsis        nevadensis, Coptotermes formosanus.    -   Bristletails, such as Lepisma saccarina.

Industrial materials in the present connection are to be understood asmeaning non-living materials, such as, preferably, plastics, adhesives,sizes, papers and cards, leather, wood and processed wood products andcoating compositions.

Wood and processed wood products are materials to be protected,especially preferably, from insect infestation.

Wood and processed wood products which can be protected by the agentsaccording to the invention or mixtures comprising these are to beunderstood as meaning, for example:

-   -   building timber, wooden beams, railway sleepers, bridge        components, boat jetties, wooden vehicles, boxes, pallets,        containers, telegraph poles, wood panelling, wooden window        frames and doors, plywood, chipboard, joinery or wooden products        which are used quite generally in house-building or in building        joinery.

The active compounds according to the invention can be used as such, inthe form of concentrates or in generally customary formulations, such aspowders, granules, solutions, suspensions, emulsions or pastes.

The formulations mentioned can be prepared in a manner known per se, forexample by mixing the active compounds according to the invention withat least one solvent or diluent, emulsifier, dispersing agent and/orbinder or fixing agent, a water repellent, if appropriate siccatives andUV stabilizers and if appropriate dyestuffs and pigments, and also otherprocessing auxiliaries.

The insecticidal compositions or concentrates used for the preservationof wood and wood-derived timber products comprise the active compoundaccording to the invention in a concentration of 0.0001 to 95% byweight, in particular 0.001 to 60% by weight.

The amount of the compositions or concentrates employed depends on thenature and occurrence of the insects and on the medium. The optimumamount employed can be determined for the use in each case by series oftests. In general, however, it is sufficient to employ 0.0001 to 20% byweight, preferably 0.001 to 10% by weight, of the active compound, basedon the material to be preserved.

Solvents and/or diluents which are used are an organic chemical solventor solvent mixture and/or an oily or oil-like organic chemical solventor solvent mixture of low volatility and/or a polar organic chemicalsolvent or solvent mixture and/or water, and if appropriate anemulsifier and/or wetting agent.

Organic chemical solvents which are preferably used are oily or oil-likesolvents having an evaporation number above 35 and a flashpoint above30° C., preferably above 45° C. Substances which are used as such oilyor oil-like water-insoluble solvents of low volatility are appropriatemineral oils or aromatic fractions thereof, or solvent mixturescontaining mineral oils, preferably white spirit, petroleum and/oralkylbenzene.

Mineral oils having a boiling range from 170 to 220° C., white spirithaving a boiling range from 170 to 220° C., spindle oil having a boilingrange from 250 to 350° C., petroleum and aromatics having a boilingrange from 160 to 280° C., terpentine oil and the like, areadvantageously employed.

In a preferred embodiment, liquid aliphatic hydrocarbons having aboiling range from 180 to 210° C. or high-boiling mixtures of aromaticand aliphatic hydrocarbons having a boiling range from 180 to 220° C.and/or spindle oil and/or monochloronaphthalene, preferablyα-monochloronaphthalene, are used.

The organic oily or oil-like solvents of low volatility which have anevaporation number above 35 and a flashpoint above 30° C., preferablyabove 45° C., can be replaced in part by organic chemical solvents ofhigh or medium volatility, provided that the solvent mixture likewisehas an evaporation number above 35 and a flashpoint above 30° C.,preferably above 45° C., and that the insecticide/fungicide mixture issoluble or emulsifiable in this solvent mixture.

According to a preferred embodiment, some of the organic chemicalsolvent or solvent mixture is replaced by an aliphatic polar organicchemical solvent or solvent mixture. Aliphatic organic chemical solventscontaining hydroxyl and/or ester and/or ether groups, such as, forexample, glycol ethers, esters or the like, are preferably used.

Organic chemical binders which are used in the context of the presentinvention are the synthetic resins and/or binding drying oils which areknown per se, are water-dilutable and/or are soluble or dispersible oremulsifiable in the organic chemical solvents employed, in particularbinders consisting of or comprising an acrylate resin, a vinyl resin,for example polyvinyl acetate, polyester resin, polycondensation orpolyaddition resin, polyurethane resin, alkyd resin or modified alkydresin, phenolic resin, hydrocarbon resin, such as indene-coumaroneresin, silicone resin, drying vegetable oils and/or drying oils and/orphysically drying binders based on a natural and/or synthetic resin.

The synthetic resin used as the binder can be employed in the form of anemulsion, dispersion or solution. Bitumen or bituminous substances canalso be used as binders in an amount of up to 10% by weight. Dyestuffs,pigments, water-repelling agents, odour correctants and inhibitors oranticorrosive agents and the like which are known per se canadditionally be employed.

It is preferred according to the invention for the composition orconcentrate to comprise, as the organic chemical binder, at least onealkyd resin or modified alkyd resin and/or a drying vegetable oil. Alkydresins having an oil content of more than 45% by weight, preferably 50to 68% by weight, are preferably used according to the invention.

All or some of the binder mentioned can be replaced by a fixing agent(mixture) or a plasticizer (mixture). These additives are intended toprevent evaporation of the active compounds and crystallization orprecipitation. They preferably replace 0.01 to 30% of the binder (basedon 100% of the binder employed).

The plasticizers originate from the chemical classes of phthalic acidesters, such as dibutyl, dioctyl or benzyl butyl phthalate, phosphoricacid esters, such as tributyl phosphate, adipic acid esters, such asdi-(2-ethylhexyl) adipate, stearates, such as butyl stearate or amylstearate, oleates, such as butyl oleate, glycerol ethers or highermolecular weight glycol ethers, glycerol esters and p-toluenesulphonicacid esters.

Fixing agents are based chemically on polyvinyl alkyl ethers, such as,for example, polyvinyl methyl ether or ketones, such as benzophenone orethylenebenzophenone.

Possible solvents or diluents are, in particular, also water, ifappropriate as a mixture with one or more of the abovementioned organicchemical solvents or diluents, emulsifiers and dispersing agents.

Particularly effective preservation of wood is achieved by impregnationprocesses on a large industrial scale, for example vacuum, double vacuumor pressure processes.

The ready-to-use compositions can also comprise other insecticides, ifappropriate, and also one or more fungicides, if appropriate.

Possible additional mixing partners are, preferably, the insecticidesand fungicides mentioned in WO 94/29 268. The compounds mentioned inthis document are an explicit constituent of the present application.

Especially preferred mixing partners which may be mentioned areinsecticides, such as chlorpyriphos, phoxim, silafluofin, alphamethrin,cyfluthrin, cypermethrin, deltamethrin, permethrin, imidacloprid, NI-25,flufenoxuron, hexaflumuron, transfluthrin, thiacloprid, methoxyfenozideand triflumuron,

-   -   and also fungicides, such as epoxyconazole, hexaconazole,        azaconazole, propiconazole, tebuconazole, cyproconazole,        metconazole, imazalil, dichlorfluanid, tolylfluanid,        3-iodo-2-propinyl-butyl carbamate, N-octyl-isothiazolin-3-one        and 4,5-dichloro-N-octylisothiazolin-3-one.

The compounds according to the invention can at the same time beemployed for protecting objects which come into contact with saltwateror brackish water, such as hulls, screens, nets, buildings, moorings andsignalling systems, against fouling.

Fouling by sessile Oligochaeta, such as Serpulidae, and by shells andspecies from the Ledamorpha group (goose barnacles), such as variousLepas and Scalpellum species, or by species from the Balanomorpha group(acorn barnacles), such as Balanus or Pollicipes species, increases thefrictional drag of ships and, as a consequence, leads to a markedincrease in operation costs owing to higher energy consumption andadditionally frequent residence in the dry dock.

Apart from fouling by algae, for example Ectocarpus sp. and Ceramiumsp., fouling by sessile Entomostraka groups, which come under thegeneric term Cirripedia (cirriped crustaceans), is of particularimportance. Surprisingly, it has now been found that the compoundsaccording to the invention, alone or in combination with other activecompounds, have an outstanding antifouling action.

Using the compounds according to the invention, alone or in combinationwith other active compounds, allows the use of heavy metals such as, forexample, in bis(trialkyltin) sulphides, tri-n-butyltin laurate,tri-n-butyltin chloride, copper(I) oxide, triethyltin chloride,tri-n-butyl(2-phenyl-4-chlorophenoxy)tin, tributyltin oxide, molybdenumdisulphide, antimony oxide, polymeric butyl titanate,phenyl-(bispyridine)-bismuth chloride, tri-n-butyltin fluoride,manganese ethylenebisthio-carbamate, zinc dimethyldithiocarbamate, zincethylenebisthiocarbamate, zinc salts and copper salts of 2-pyridinethiol1-oxide, bisdimethyldithiocarbamoylzinc ethylene-bisthiocarbamate, zincoxide, copper(I) ethylene-bisdithiocarbamate, copper thiocyanate, coppernaphthenate and tributyltin halides to be dispensed with, or theconcentration of these compounds to be substantially reduced.

If appropriate, the ready-to-use antifouling paints can additionallycomprise other active compounds, preferably algicides, fungicides,herbicides, molluscicides, or other antifouling active compounds.

Preferably suitable components in combinations with the antifoulingcompositions according to the invention are:

-   -   algicides such as    -   2-tert-butylamino-4-cyclopropylamino-6-methylthio-1,3,5-triazine,        dichlorophen, diuron, endothal, fentin acetate, isoproturon,        methabenzthiazuron, oxyfluorfen, quinoclamine and terbutryn;    -   fungicides such as    -   benzo[b]thiophenecarboxylic acid cyclohexylamide S,S-dioxide,        dichlofluanid, fluorfolpet, 3-iodo-2-propinyl butylcarbamate,        tolylfluanid and azoles such as azaconazole, cyproconazole,        epoxyconazole, hexaconazole, metconazole, propiconazole and        tebuconazole;    -   molluscicides such as    -   fentin acetate, metaldehyde, methiocarb, niclosamid, thiodicarb        and trimethacarb;    -   or conventional antifouling active compounds such as    -   4,5-dichloro-2-octyl-4-isothiazolin-3-one, diiodomethylparatryl        sulphone, 2-(N,N-dimethylthiocarbamoylthio)-5-nitrothiazyl,        potassium, copper, sodium and zinc salts of 2-pyridinethiol        1-oxide, pyridine-triphenylborane, tetrabutyldistannoxane,        2,3,5,6-tetrachloro-4-(methylsulphonyl)-pyridine,        2,4,5,6-tetrachloroisophthalonitrile, tetramethylthiuram        disulphide and 2,4,6-trichlorophenylmaleimide.

The antifouling compositions used comprise the active compound accordingto the invention of the compounds according to the invention in aconcentration of 0.001 to 50% by weight, in particular 0.01 to 20% byweight.

Moreover, the antifouling compositions according to the inventioncomprise the customary components such as, for example, those describedin Ungerer, Chem. Ind. 1985, 37, 730-732 and Williams, AntifoulingMarine Coatings, Noyes, Park Ridge, 1973.

Besides the algicidal, fungicidal, molluscicidal active compounds andinsecticidal active compounds according to the invention, antifoulingpaints comprise, in particular, binders.

Examples of recognized binders are polyvinyl chloride in a solventsystem, chlorinated rubber in a solvent system, acrylic resins in asolvent system, in particular in an aqueous system, vinyl chloride/vinylacetate copolymer systems in the form of aqueous dispersions or in theform of organic solvent systems, butadiene/-styrene/acrylonitrilerubbers, drying oils such as linseed oil, resin esters or modifiedhardened resins in combination with tar or bitumens, asphalt and epoxycompounds, small amounts of chlorine rubber, chlorinated polypropyleneand vinyl resins.

If appropriate, paints also comprise inorganic pigments, organicpigments or colorants which are preferably insoluble in salt water.Paints may furthermore comprise materials such as colophonium to allowcontrolled release of the active compounds. Furthermore, the paints maycomprise plasticizers, modifiers which affect the rheological propertiesand other conventional constituents. The compounds according to theinvention or the abovementioned mixtures may also be incorporated intoself-polishing antifouling systems.

The active compounds according to the invention are also suitable forcontrolling animal pests, in particular insects, arachnids and mites,which are found in enclosed spaces such as, for example, dwellings,factory halls, offices, vehicle cabins and the like. They can beemployed alone or in combination with other active compounds andauxiliaries in domestic insecticide products for controlling thesepests. They are active against sensitive and resistant species andagainst all development stages. These pests include:

-   -   From the order of the Scorpionidea, for example, Buthus        occitanus.    -   From the order of the Acarina, for example, Argas persicus,        Argas reflexus, Bryobia spp., Dermanyssus gallinae, Glyciphagus        domesticus, Ornithodorus moubat, Rhipicephalus sanguineus,        Trombicula alfreddugesi, Neutrombicula autumnalis,        Dermatophagoides pteronissimus and Dermatophagoides forinae.    -   From the order of the Araneae, for example, Aviculariidae and        Araneidae.    -   From the order of the Opiliones, for example, Pseudoscorpiones        chelifer, Pseudoscorpiones cheiridium and Opiliones phalangium.    -   From the order of the Isopoda, for example, Oniscus asellus and        Porcellio scaber.    -   From the order of the Diplopoda, for example, Blaniulus        guttulatus and Polydesmus spp.    -   From the order of the Chilopoda, for example, Geophilus spp.    -   From the order of the Zygentoma, for example, Ctenolepisma spp.,        Lepisma saccharina and Lepismodes inquilinus.    -   From the order of the Blattaria, for example, Blatta        orientalies, Blattella germanica, Blattella asahinai, Leucophaea        maderae, Panchlora spp., Parcoblatta spp., Periplaneta        australasiae, Periplaneta americana, Periplaneta brunnea,        Periplaneta fuliginosa and Supella longipalpa.    -   From the order of the Saltatoria, for example, Acheta        domesticus.    -   From the order of the Dermaptera, for example, Forficula        auricularia.    -   From the order of the Isoptera, for example, Kalotermes spp. and        Reticulitermes spp.    -   From the order of the Psocoptera, for example, Lepinatus spp.        and Liposcelis spp.    -   From the order of the Coleptera, for example, Anthrenus spp.,        Attagenus spp., Dermestes spp., Latheticus oryzae, Necrobia        spp., Ptinus spp., Rhizopertha dominica, Sitophilus granarius,        Sitophilus oryzae, Sitophilus zeamais and Stegobium paniceum.    -   From the order of the Diptera, for example, Aedes aegypti, Aedes        albopictus, Aedes taeniorhynchus, Anopheles spp., Calliphora        erythrocephala, Chrysozona pluvialis, Culex quinquefasciatus,        Culex pipiens, Culex tarsalis, Drosophila spp., Fannia        canicularis, Musca domestica, Phlebotomus spp., Sarcophaga        carnaria, Simulium spp., Stomoxys calcitrans and Tipula        paludosa.    -   From the order of the Lepidoptera, for example, Achroia        grisella, Galleria mellonella, Plodia interpunctella, Tinea        cloacella, Tinea pellionella and Tineola bisselliella.    -   From the order of the Siphonaptera, for example, Ctenocephalides        canis, Ctenocephalides felis, Pulex irritans, Tunga penetrans        and Xenopsylla cheopis.    -   From the order of the Hymenoptera, for example, Camponotus        herculeanus, Lasius fuliginosus, Lasius niger, Lasius umbratus,        Monomorium pharaonis, Paravespula spp. and Tetramorium        caespitum.    -   From the order of the Anoplura, for example, Pediculus humanus        capitis, Pediculus humanus corporis and Phthirus pubis.    -   From the order of the Heteroptera, for example, Cimex        hemipterus, Cimex lectularius, Rhodinus prolixus and Triatoma        infestans.

In the field of household insecticides, they are used alone or incombination with other suitable active compounds, such as phosphoricacid esters, carbamates, pyrethroids, growth regulators or activecompounds from other known classes of insecticides.

They are used as aerosols, pressure-free spray products, for examplepump and atomizer sprays, automatic fogging systems, foggers, foams,gels, evaporator products with evaporator tablets made of cellulose orpolymer, liquid evaporators, gel and membrane evaporators,propeller-driven evaporators, energy-free, or passive evaporationsystems, moth papers, moth bags and moth gels, as granules or dusts, inbaits for spreading or in bait stations.

The preparation and use of the substances according to the invention isshown in the examples below.

PREPARATION EXAMPLES Example 1

5-(2,6-Difluorophenyl)-2-[4-(4,4,5,5-tetramethyl-1,3,2-dioxaborolan-2-yl)phenyl]-3,4-dihydro-2H-pyrrole(0.96 g, 2.50 mmol) is introduced in 1,2-dimethoxyethane (70 ml) underan argon atmosphere. Added in succession are 5-bromo-2-ethoxypyridine(III-1) (0.61 g, 3.00 mmol),1,1′-bis(diphenylphosphino)ferrocenepalladium(II) chloride (0.05 g, 0.07mol) and 3.75 ml of sodium carbonate solution (20% strength, w/v). Thereaction mixture is allowed to continue reaction at 80° C. for 16 h.

Thereafter, water/ethyl acetate are added to the reaction mixture andthe organic phase is separated off, dried over sodium sulphate,filtered, mixed with 5 g of Florisil and concentrated. The crude productis purified by chromatography on silica gel (mobile phase:n-hexane/ethyl acetate 4:1).

This gives 0.68 g (67% of theory) of5-{4-[5-(2,6-difluorophenyl)-3,4-dihydro-2H-pyrrol-2-yl]phenyl}-2-ethoxypyridine.

HPLC: logP (pH 2.3)=2.92

NMR (CD₃CN): δ=1.3-1.4 (t, 3H), 1.8-1.9 (m, 1H), 2.7 (m, 1H), 3.0-3.1(m, 2H), 4.3-4.4 (m, 2H), 5.3 (m, 1H), 6.8 (d, 1H), 7.0-7.1 (t, 2H),7.3-7.4 (m, 3H), 7.4 (d, 2H), 7.9 (m, 1H), 8.4 (d, 1H) ppm.

In analogy to Example 1 and in accordance with the general descriptionsof processes (A), (B), (C) or (D) the compounds listed in the tablebelow can be prepared. (I)

No. R¹ R² Y R³ log P 2 F F O Methyl 3 F F S Methyl 4 F F S Ethyl3.29^(a)), 4.54^(b)) 5 F F O n-Propyl 3.42^(a)), 4.77^(b)) 6 F F Sn-Propyl 7 F F O i-Propyl 3.42^(a)), 4.73^(b)) 8 F F S i-Propyl3.80^(a)), 4.96^(b)) 9 F F O n-Butyl 10 F F S n-Butyl 11 F F O i-Butyl12 F F S i-Butyl 13 F F O s-Butyl 14 F F S s-Butyl 15 F F O t-Butyl3.94^(a)) 16 F F S t-Butyl 17 F F O Cyclopropyl 18 F F S Cyclopropyl 19F F O Cyclobutyl 3.66^(a)), 4.90^(b)) 20 F F S Cyclobutyl 21 F F OCyclopentyl 3.99^(a)), 5.34^(b)) 22 F F S Cyclopentyl 23 F F OCyclohexyl 24 F F S Cyclohexyl 25 F F O Cyclopropylmethyl 3.48^(a)),4.67^(b)) 26 F F S Cyclopropylmethyl 27 F F O Cyclobutylmethyl 28 F F SCyclobutylmethyl 29 F F O Cyclopentylmethyl 30 F F S Cyclopentylmethyl31 F F O Cyclohexylmethyl 32 F F S Cyclohexylmethyl 33 F F OCyclopropylethyl 34 F F S Cyclopropylethyl 35 F F O Cyclobutylethyl 36 FF S Cyclobutylethyl 37 F F O Cyclopentylethyl 38 F F S Cyclopentylethyl39 F F O Cyclohexylethyl 40 F F S CyclohexylethylPreparation of Starting Materials of the Formula (III)

Example III-1

0.49 g (20.26 mmol) of sodium hydride is introduced under argon andcooled to 10° C. 10 ml of dimethylformamide are added. Subsequently asolution of 0.93 g (20.26 mmol) of ethanol in 40 ml of dimethylformamideis added slowly dropwise and reaction is allowed to continue for 30minutes. Thereafter 4.00 g (16.89 mmol) of 2,5-dibromopyridine are addeddropwise and reaction is allowed to continue for a further 16 hours.

Water is added to the reaction mixture. It is extracted three times withethyl acetate. The organic phase is washed once with sodium hydrogencarbonate solution and once with sodium chloride solution, dried oversodium sulphate, filtered and concentrated.

This gives 2.35 g (67% of theory) of 5-bromo-2-ethoxypyridine.

HPLC: logP (pH 2.3)=2.92

NMR (CD₃CN): δ=1.33 (t, 3H), 4.27-4.32 (m, 2H), 6.68 (d, 1H), 7.75 (m,1H), 8.2 (d, 1H) ppm.

The log p values reported in the above tables and preparation examplesare determined in accordance with EEC Directive 79/831 Annex V.A8 bymeans of HPLC (high performance liquid chromatography) on areversed-phase column (C 18). Temperature: 43° C.

Determination is carried out in the acidic range at a pH of 2.3 using0.1% aqueous phosphoric acid and acetonitrile as mobile phases; lineargradient from 10% acetonitrile to 90% acetonitrile. The values aremarked in the tables with ^(a)).

Determination takes place in the neutral range at a pH of 7.5 with0.01-molar aqueous phosphate buffer solution and acetonitrile as mobilephases; linear gradient from 10% acetonitrile to 90% acetonitrile. Thevalues are marked in the tables with ^(b)).

The calibration is carried out using unbranched alkan-2-ones (havingfrom 3 to 16 carbon atoms) whose logP values are known (logP valuesdetermined on the basis of the retention times, using linearinterpolation between two successive alkanones).

The lambda max values were determined in the maxima of thechromatographic signals using the UV spectra from 200 nm to 400 nm.

USE EXAMPLES Example A

Aphis gossypii test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cotton leaves (Gossypium hirsutum) heavily infested by the cotton aphid(Aphis gossypii) are treated by being dipped into the preparation ofactive compound of the desired concentration.

After the desired period of time, the kill in % is determined. 100%means that all aphids have been killed; 0% means that none of the aphidshas been killed.

In this test, for example, the following compounds from the preparationexamples display good activity: TABLE A Plant-damaging insects Aphisgossypii test Active compound Efficacy No. Active compoundsconcentration in ppm in % after 6^(d) 5

100 99 7

100 99

Example B

Heliothis armigera test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Soya bean shoots (Glycine max) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with caterpillars of the cotton bollworm (Heliothis armigera)whilst the leaves are still moist. After the desired period of time, thekill in % is determined. 100% means that all aphids have been killed; 0%means that none of the caterpillars has been killed.

In this test, for example, the following compounds from the preparationexamples display good activity: TABLE B Plant-damaging insects Heliothislarvae test Active compound Efficacy No. Active compounds concentrationin ppm in % after 7^(d) 15

20 100 25

20 100

Example C

Heliothis virescens test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Soya bean shoots (Glycine max) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with Heliothis virescens caterpillars whilst the leaves arestill moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

In this test, for example, the following compounds in the preparationexamples display good activity: TABLE C Plant-damaging insects Heliothisvirescens test Active compound Efficacy No. Active compoundsconcentration in ppm in % after 7^(d) 5

100 100 4

100 100 8

100 100 7

100 100

Example D

Phaedon larvae test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with larvae of the mustard beetle (Phaedon cochleariae) whilstthe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all beetle larvae have been killed; 0% means that none of thebeetle larvae has been killed.

In this test, for example, the following compounds from the preparationexamples display superior activity as compared with the prior art: TABLED Plant-damaging insects Phaedon larvae test Active compound EfficacyNo. Active compounds concentration in ppm in % after 7^(d) 1

100 100 5

100 100 4

100 100 8

100 100 7

100 100 15

100 100 21

100 100 25

100 100 19

20 100

Example E

Plutella test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with cabbage moth (Plutella xylostella) caterpillars whilstthe leaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

In this test, for example, the following compounds from the preparationexamples display good activity: TABLE E Plant-damaging insects Plutellatest Active compound Efficacy No. Active compounds concentration in ppmin % after 7^(d) 5

100 100 4

100 100 8

100 100 7

100 100 15

20 100 25

20 100

Example F

Spodoptera exigua test Solvent: 7 parts by weight of dimethylformamideEmulsifier: 2 parts by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with army worm (Spodoptera exigua) caterpillars whilst theleaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

In this test, for example, the following compounds from the preparationexamples display good activity: TABLE F Plant-damaging insectsSpodoptera exigua larvae test Active compound Efficacy No. Activecompounds concentration in ppm in % after 7^(d) 5

100 100 4

100 100 8

100 100 7

100 100 15

20 100 25

20 100

Example G

Spodoptera frugiperda test Solvent: 7 parts by weight ofdimethylformamide Emulsifier: 2 parts by weight of alkylaryl polyglycolether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Cabbage leaves (Brassica oleracea) are treated by being dipped into thepreparation of active compound of the desired concentration and arepopulated with army worm (Spodoptera frugiperda) caterpillars whilst theleaves are still moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

In this test, for example, the following compounds from the preparationexamples display good activity: TABLE G Plant-damaging insectsSpodoptera frugiperda test Active compound Efficacy No. Active compoundsconcentration in ppm in % after 7^(d) 1

100 100 5

100 100 4

100 100 8

100 100 7

100 100 15

100 100 21

100 100 25

100 100 19

100 100

Example H

Tetranychus test (OP resistant/dip treatment) Solvent: 7 parts by weightof dimethylformamide Emulsifier: 2 parts by weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Bean plants (Phaseolus vulgaris) which are heavily infested by allstages of the greenhouse red spider mite (Tetranychus urticae) aredipped into a preparation of active compound of the desiredconcentration.

After the desired period of time, the effect in % is determined. 100%means that all spider mites have been killed; 0% means that none of thespider mites has been killed.

In this test, for example, the following compounds from the preparationexamples display good activity: TABLE H Plant-damaging mitesTetranychus-Test (OP-resistant/dip treatment) Active compound EfficacyNo. Active compounds concentration in ppm in % after 7^(d) 5

100 98 4

100 95 8

100 98 21

100 95 15

100 95 19

100 95

Example I

Panonychus test Solvent: 3 parts by weight of dimethylformamideEmulsifier: 1 part by weight of alkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amounts of solvent andemulsifier, and the concentrate is diluted with emulsifier-containingwater to the desired concentration.

Plum trees (Prunus domestica) about 30 cm high which are heavilyinfested by all stages of the fruit tree red spider mite (Panonychusulmi) are dipped into a preparation of active compound of the desiredconcentration.

After the desired period of time, the effect in % is determined. 100%means that all spider mites have been killed; 0% means that none of thespider mites has been killed.

In this test, for example, the following compounds from the preparationexamples display good activity: TABLE I Plant-damaging mites Panonychustest Active compound Efficacy No. Active compound concentration in ppmin % after 7^(d) 7

100 100

Example K

Diabrotica balteata test (larvae in soil) Critical concentrationtest/soil insects - treatment of transgenic plants Solvent: 7 parts byweight of dimethylformamide Emulsifier: 1 part by weight of alkylarylpolyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent, thestated amount of emulsifier is added and the concentrate is diluted withwater to the desired concentration.

The preparation of active compound is poured onto the soil. Here, theconcentration of the active compound in the preparation is virtuallyimmaterial, only the amount by weight of active compound per volume unitof soil, which is stated in ppm (mg/l), matters. The soil is filled into0.25 l pots, and these are allowed to stand at 20° C.

Immediately after the preparation, 5 pregerminated maize corns of thecultivar YIELD GUARD (trade mark of Monsanto Comp., USA) are placed intoeach pot. After 2 days, the corresponding test insects are placed intothe treated soil. After a further 7 days, the efficacy of the activecompound is determined by counting the number of maize plants that haveemerged (1 plant=20% activity).

Example L

Heliothis virescens test (treatment of transgenic plants) Solvent: 7parts by weight of dimethylformamide Emulsifier: 1 part by weight ofalkylaryl polyglycol ether

To produce a suitable preparation of active compound, 1 part by weightof active compound is mixed with the stated amount of solvent and thestated amount of emulsifier, and the concentrate is diluted with waterto the desired concentration.

Soya bean shoots (Glycine max) of the cultivar Roundup Ready (trade markof Monsanto Comp. USA) are treated by being dipped into the preparationof active compound of the desired concentration and populated with thetobacco budworm caterpillar Heliothis virescens whilst the leaves arestill moist.

After the desired period of time, the kill in % is determined. 100%means that all caterpillars have been killed; 0% means that none of thecaterpillars has been killed.

Example M

Blowfly larvae test/development-inhibiting effect Test organisms:Lucilia cuprina larvae Solvent: Dimethyl sulphoxide

20 mg of active compound are dissolved in 1 ml of dimethyl sulphoxide;lower concentrations are prepared by dilution with distilled water.

About 20 Lucilia cuprina larvae are introduced into a test tubecontaining about 1 cm³ of horse meat and 0.5 ml of the test preparationof active compound. After 24 and 48 hours, the activity of thepreparation is determined. The test tubes are transferred to beakerswith their bases covered with sand. After a further 14 days, the testtubes are removed and the pupae/flies are counted.

The effect of the preparation is assessed according to the number offlies which have hatched after 1.5 times the development period of anuntreated control. 100% means that no flies have hatched; 0% means thatall of the flies have hatched normally.

In this test, for example, the following compounds from the preparationexamples display good activity: TABLE M Blowfly larvaetest/development-inhibiting action Active compound % Activity/ No.Active compound concentration in ppm kill (48 h) 25

100 100 Active compound % Activity/ No. Active compounds concentrationin ppm kill (14 d) 25

 20 100 19

100/20 100/100  4

100 100

1-14. (canceled)
 15. A Δ¹-pyrroline of formula (I)

in which R¹ is halogen or methyl, R² is hydrogen or halogen, Y is O orS, and R³ is C₁-C₄-alkyl, C₃-C₆-cycloalkyl, orC₃-C₆-cycloalkyl-C₁-C₂-alkyl.
 16. A Δ¹-pyrroline of formula (I)according to claim 15 in which R¹ is fluorine, chlorine, or methyl, R²is hydrogen, fluorine, or chlorine, Y is O or S, and R³ is C₁-C₄-alkyl,C₃-C₆-cycloalkyl, or C₃-C₆-cycloalkyl-C₁-C₂-alkyl.
 17. A Δ¹-pyrroline offormula (I) according to claim 15 in which R¹ is fluorine or chlorine,R² is hydrogen, fluorine, or chlorine, Y is O or S, and R³ is methyl,ethyl, propyl, butyl, cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl,cyclopropyl-C₁-C₂-alkyl, cyclobutyl-C₁-C₂-alkyl,cyclopentyl-C₁-C₂-alkyl, or cyclohexyl-C₁-C₂-alkyl.
 18. A Δ¹-pyrrolineof formula (I) according to claim 15 in which R¹ is fluorine orchlorine, R² is hydrogen or fluorine, Y is O or S, and R³ is methyl,ethyl, n-propyl, iso-propyl, n-butyl, iso-butyl, sec-butyl, tert-butyl,cyclopropyl, cyclobutyl, cyclopentyl, cyclohexyl, cyclopropylmethyl,cyclobutylmethyl, cyclopentylmethyl, cyclohexylmethyl, cyclopropylethyl,cyclobutylethyl, cyclopentylethyl, or cyclohexylethyl.
 19. AΔ¹-pyrroline of formula (I) according to claim 15 in which R¹ and R² arefluorine.
 20. A Δ¹-pyrroline of formula (I) according to claim 15 inwhich Y is oxygen.
 21. A Δ¹-pyrroline of formula (I) according to claim15 in which Y is sulphur.
 22. A Δ¹-pyrroline of formula (I) according toclaim 15 in which R³ is C₁-C₄-alkyl.
 23. An (R)-configured compound offormula (I-a)

in which R¹, R², and R³ as defined for formula (I) in claim
 15. 24. Aprocess for preparing a compound of formula (I) according to claim 15comprising (A) reacting, in a tandem reaction, a Δ¹-pyrroline of formula(ii)

in which R¹ and R² are as defined for formula (I) in claim 15, and Z ischlorine, bromine, iodine, —OSO₂CF₃, or —OSO₂(CF₂)₃CF₃, with aheterocycle of formula (III)

in which Y and R³ are as defined for formula (I) in claim 15, and X ischlorine, bromine, iodine, —OSO₂CF₃ or —OSO₂(CF₂)₃CF₃, in the presenceof a catalyst, in the presence of a diboronic ester, optionally in thepresence of an acid binder, and optionally in the presence of a diluent,or (B) reacting a Δ¹-pyrroline of formula (IV)

in which R¹ and R² are as defined for formula (I) in claim 15, and A is—B(OH)₂, (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or 1,3,2-benzodioxaborol-2-yl,with a heterocycle of formula (III)

in which Y and R³ are as defined for formula (I) in claim 15, and X ischlorine, bromine, iodine, —OSO₂CF₃ or —OSO₂(CF₂)₃CF₃, in the presenceof a catalyst, optionally in the presence of an acid binder, andoptionally in the presence of a diluent, or (C) reacting a Δ¹-pyrrolineof formula (II)

in which R¹ and R² are as defined for formula (I) in claim 15, and Z ischlorine, bromine, iodine, —OSO₂CF₃, or —OSO₂(CF₂)₃CF₃, with a boronicacid derivative of formula (V)

in which Y and R³ are as defined for formula (I) in claim 15, and A is—B(OH)₂, (4,4,5,5-tetramethyl-1,3,2-dioxaborolan)-2-yl,(5,5-dimethyl-1,3,2-dioxaborinan)-2-yl,(4,4,6-trimethyl-1,3,2-dioxaborinan)-2-yl or 1,3,2-benzodioxaborol-2-yl,in the presence of a catalyst, optionally in the presence of an acidbinder, and optionally in the presence of a diluent, or (D) reacting aΔ¹-pyrroline of formula (II-a)

in which R¹ and R² are as defined for formula (I) in claim 15, and Z¹ isbromine or iodine, with an organometallic compound of formula (VI)

in which Y and R³ are as defined for formula (I) in claim 15, and M isZnCl, Sn(Me)₃, or Sn(n-Bu)₃, in the presence of a catalyst, optionallyin the presence of an acid binder, and optionally in the presence of adiluent.
 25. A pesticide comprising one or more compounds of formula (I)according to claim 15 and one or more extenders and/or surface-activesubstances.
 26. A method of controlling pests comprising causing aneffective amount of one or more compounds of formula (I) according toclaim 15 to act on pests and/or their habitat.
 27. A process forpreparing pesticides comprising mixing one or more compounds of formula(I) according to claim 15 with one or more extenders and/orsurface-active substances.